Alcohol composition and derivatives thereof

ABSTRACT

The invention provides a composition comprising a mixture of pentadecanols wherein at least about 60 wt % of the mixture is linear pentadecanol and at least about 10 wt % of the mixture is branched pentadecanols wherein the branched pentadecanols have branching on the second carbon atom. The mixture of pentadecanols may be converted to one or more derivatives, and these derivatives may be used in laundry detergents, cleaning products or as an agricultural adjuvant, an emulsifying agent, a lubricant additive, a pour point depressant, or a personal care ingredient.

The present application claims the benefit of U. S. Provisional PatentApplication Ser. No. 62/270,611, filed Dec. 22, 2015.

FIELD OF THE INVENTION

The present invention relates to an alcohol composition comprisingpentadecanols and derivatives thereof.

BACKGROUND OF THE INVENTION

Pentadecanols are well known in commerce as components of a variety ofcommercially available fatty alcohol blends. These blends generallyconsist of fatty alcohols spanning a range of molecular weights. Forexample, NEODOL® 45 contains mainly alcohols with 14 or 15 carbons;NEODOL 25 contains mainly alcohols with 12, 13, 14, or 15 carbons.

Normal 1-pentadecanol is well known as a fragrance and flavoringingredient as well as a skin emollient ingredient. It is most commonlyobtained by extraction from vegetable materials. For example, it can beobtained from a CO₂ extract of angelica seed oil. It can also beobtained from hydrodistilled oil obtained from the stem bark of Myricaesculenta Buch. Ham. ex D. Don (Nat Prod Res. 2012; 26(23):2266-9). Itis known to have specific activity against Proponibacterium acnes(Journal of Natural Products Vol. 57, No. 1, pp. 9-17, January 1994) andcan be used as a topical treatment for acne vulgaris (U.S. Pat. No.5,380,763). Its extraction from vegetable sources limits availabilityand results in high cost.

A second type of primary pentadecanol is produced by performing the oxohydroformylation reaction on a linear tetradecene as disclosed in U.S.Pat. No. 7,183,446. This yields a pentadecanol mixture containing 40% orgreater of branched species. While this route provides betteravailability and reduced cost, it yields branched species that may haveundesirable properties in some applications if substituted for normal1-pentadecanol. If this type of pentadecanol is used as a skin emollientor to synthesize useful derivatives like surface active agents, the highdegree of branching may limit its functionality in these uses. There isa need for a pentadecanol with a lower proportion of branched speciesthat can be produced in volume and at reasonable cost.

SUMMARY OF THE INVENTION

The invention provides a composition comprising a mixture ofpentadecanols wherein at least about 60 wt % of the mixture is linearpentadecanol and at least about 10 wt % of the mixture is branchedpentadecanols wherein the branched pentadecanols have branching on thesecond carbon atom.

The mixture of pentadecanols may be converted to one or morederivatives, and these derivatives may be used in laundry detergents,cleaning products or as an agricultural adjuvant, an emulsifying agent,a lubricant additive, a pour point depressant, or a personal careingredient.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a pentadecanol with a low degree ofbranching and derivatives made therefrom. The more elongated and lessbulky molecular character of this pentadecanol confers superiorcharacteristics to derivatives derived from it. This is particularlyapparent in surface active agent derivatives. Surface active agents madewith this pentadecanol are expected to exhibit better detergency andsoil adsorption than similar surface active agents made with more highlybranched pentadecanols. In addition they are likely to be more readilybiodegraded in the environment.

The present invention provides a mixture of primary pentadecanolswherein at least about 60 wt % of the mixture is linear pentadecanol andat least about 10 wt % of the mixture is branched pentadecanols whereinthe branched pentadecanols have branching on the second carbon atom. Themixture may contain at least about 70 wt % linear pentadecanols. Themixture may contain at least about 15 wt % branched pentadecanols.

The derivatives of the pentadecanols include esters of dicarboxylicacids or other polyacids useful as plasticizers as well as alkoxylatedalcohols, sulfated alcohols, sulfated alkoxylated alcohols, alcoholether amines, or other derivatives with hydrophilic moieties useful assurface active agents.

Linear pentadecanols have the structure (1):

H—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—CH₂—OH   (1)

Branched pentadecanols have the general structure (2):

-   -   R₂    -   I

R₁—CH—CH₂OH   (2)

where R₁ and R₂ are linear alkyl chains containing a total of 13 carbonatoms in the two alkyl chains.

Mixtures having the composition of approximately 60-90 wt % of structure(1) and 10-40 wt % of structure (2) can be synthesized from lineartetradecene by the modified Oxo process, using a phosphine, phosphite,arsine, or pyridine ligand modified cobalt or rhodium catalyst, asdescribed in U.S. Pat. Nos. 3,231,621, 3,239,566, 3,239,569, 3,239,570,3,239,571, 3,420,898, 3,440,291, 3,448,158, 3,448,157, 3,496,203,3,496,204, 3,501,515, 3,527,818, the disclosures of which areincorporated herein by reference.

Hydroformylation denotes the reaction of an olefin with CO and H₂ toproduce an aldehyde/alcohol which has one more carbon atom than thereactant olefin. The term hydroformylation may also cover the step offorming an aldehyde and the subsequent reduction to the alcohol. As usedherein, hydroformylation refers to the production of alcohols fromolefins via carbonylation and an aldehyde reduction process.

Alcohol derivatives useful as surface active agents are well known inthe art. Synthesis and properties of common surface active agents aredisclosed in Handbook of Detergents Part F: Production, Zoller, Uri andSosis, Paul CRC Press, 2009, p. 24 and references cited therein.

The present invention includes surface active agents synthesized from amixture of primary pentadecanols in which at least about 60 wt % of thealkyl chains are linear and at least about 10 wt % of the alkyl chainsare branched at the 2-carbon position. Preferred embodiments of thisinvention include polyalkoxylates, sulfates, sulfated polyalkoxylates,and ether amines of the novel pentadecanol mixture.

U.S. Pat. No. 3,440,291 describes the hydroformylation of linear alphaolefins to form mixtures of branched and linear alcohols. This processapplied to linear 1-tetradecene would yield branched and linearpentadecanols. This mixture could be separated by partialcrystallization or other methods into several fractions of differentconcentrations of branched and linear species. By combining thesefractions, several samples of pentadecanol mixtures with specifiedratios of branched/linear ratios could then be prepared. The branchingof samples (1-4) that could be made is shown in Table 1.

TABLE 1 Sample Branch to linear ratio 1 10:90 2 20:80 3 40:60 4 60:40

Household Detergent Applications

Alcohols in the range from C12 to C16 are often referred to as detergentalcohols due to the many derivatives that find use as detergentproducts. In these applications an important property is the rate atwhich the alcohol biodegrades under aerobic conditions. If an organicchemical biodegrades to a 60% level in 28 days it is considered “readilybiodegradable.” The alcohol samples 1-4 should be readily biodegradable.

Detergent derivatives of alcohols in the C12 to C16 range have manyproperties that depend on the length of the carbon chain. In soaps,carboxylate derivatives of alcohols from C12 to C14 are known for theirhigh rate of lather and degree of solubility. Carboxylate derivativesfrom C15 to C16 are known for their low rate of lather and lowsolubility. Of these the carboxylate derivatives from C12 to C14, it isknown that lathering decreases from C12 to C14 but skin irritationpotential also decreases similarly. C15 carboxylates are expected tooffer a good balance between lathering and skin irritation potential.

Alcohol sulfate surfactants in the C12 to C16 range are often used inlaundry detergent products. Similarly to the carboxylates, C12 alcoholsulfates are known to offer the best flash foam but are also theharshest to the skin. C16 alcohol sulfates are known to not foam as muchbut are milder. C15 alcohol sulfates are expected to offer a goodbalance between foaming and skin mildness. This trend is seen in manyother classes of surfactant. If choosing between a C12 derivative and aC16 derivative, often the C15 derivative would provide a goodcompromise.

The presence of low levels of branching provides a benefit to handlingthe alcohol in processing. The higher the branching content, the higherthe pour point, affording ease and economy in processing. Branching inalcohol derivatives also show benefits. In alcohol sulfates, branchingraises the Krafft point resulting in greater solubility and a broadereffective temperature range. On the opposite hand, soil removalproperties are often impacted negatively by high degrees of branching.We find that alcohols having 10-40% branching provide an optimaltradeoff between low temperature solubility and soil removal for manysurfactant derivatives.

Similar results are expected for other derivatives includingcarboxylate, sulfate, alkoxylate, and alkoxylate sulfate derivatives. Inmany cases the range of preferred properties would be demonstrated whenthe hydrophobe is C15 and the branching level is 10% to 40%. We wouldexpect to see similar results in other classes of surfactants notmentioned here. Additionally we anticipate other useful derivativemixtures could be used as an agricultural adjuvant, an emulsifyingagent, a lubricant additive, a pour point depressant, or a personal careingredient.

1. A composition comprising a mixture of pentadecanols wherein at leastabout 60 wt % of the mixture is linear pentadecanol and at least about10 wt % of the mixture is branched pentadecanols wherein the branchedpentadecanols have branching on the second carbon atom.
 2. Thecomposition of claim 1 wherein at least about 70 wt % of the mixture islinear pentadecanol.
 3. The composition of claim 1 wherein at leastabout 15 wt % of the mixture if branched pentadecanols.
 4. A compositioncomprising one or more derivatives of the pentadecanol mixture asclaimed in claim
 1. 5. The composition of claim 4 wherein thederivatives comprise esters of dicarboxylic acids, esters ofpolycarboxylic acids, alkoxylated alcohols, sulfated alcohols, sulfatedalkoxylated alcohols and alcohol ether amines
 6. The composition ofclaim 4 wherein the derivative comprises a diester of the pentadecanolmixture with one or more diacids.
 7. The composition of claim 6 whereinthe diacids comprise phthalic acid, adipic acid, sebacic acid,trimellitic acid and succinic acid.
 8. The composition of claim 4wherein the derivative comprises a polyester of the pentadecanol mixturewith one or more polyacids.
 9. The composition of claim 8 wherein thepolyacid comprises trimellitic acid.
 10. The composition of claim 4wherein the derivatives comprise a polyalkoxylate, sulfate, sulfatedpolyalkoxylate or ether amine.
 11. A hard surface cleaning formulationcomprising the composition of claim
 10. 12. A laundry detergentformulation comprising the composition of claim
 10. 13. The use of thecomposition of claim 4 as an agricultural adjuvant, an emulsifyingagent, a lubricant additive, a pour point depressant, or a personal careingredient.
 14. The composition of claim 1 wherein at least about 65 wt% of the mixture is linear pentadecanol and at least about 15 wt % ofthe mixture is branched pentadecanols.
 15. The composition of claim 1wherein from 60-80 wt % of the mixture is linear pentadecanol.
 16. Thecomposition of claim 1 wherein from 10-25 wt % of the mixture isbranched pentadecanols.